FLUIDS FOR REFRIGERANT CIRCUITS

Abstract: New refrigerant media for use in refrigeration circuits as a replacement for chlorofluorocarbons (CFCs) in view of reducing risks in connection with environmental pollution and ozone depletion in the stratosphere. Said new refrigerant media are azeotropic mixtures of isobutane (R600a) and a fluorinated hydrocarbon in a percentage ranging from 5 to 50 percent and 50 to 95 percent, respectively.

Description: FLUIDS FOR REFRIGERANT CIRCUITS DESCRIPTION The present invention refers to new refrigerant media for use in re f rigeration circuits as a replacement for chloro f luorocarbons ( CFCs ) in view o f reducing risks in connection with the environmental pollution and , in particular , the depletion of that ozone layer in the stratosphere which plays a vital role in protecting the earth against solar UV radiation . This is largely known to currently represent one among the most abundantly debated, heartfelt problems within the whole environmental protection issue , and both scienti f ic and industri al organi zat ions and authori ties are making huge efforts in searching for and experimenting with new media that may prove helpful in solving it . In this connection, one of the most frequently followed routes seems to be the identification of appropriate azeotropic mixtures. However, azeotropy is known to be an unpredictable phenomenon and the search for new azeotropic mixtures which actually have all of the properties that are required for them to be capable of being effectively used as refrigerant media, is not easy. The patent specification US-A-4 , 155 , 865 discloses an azeotropic mixture which essentially consists of approx. 69.1 to 99.5 weight-percent of 1, 1, 2 , 2-tetrafluoroethane and approx. 0.5 to 30.9 weight-percent of 1,1,1,2- tetrafluorochloroethane. However, such a mixture is still containing a fluid, ie. tetrafluorochloroethane, which has been included in the EEC Regulations no. 594/91, dated March 4, 1991, which cover substances that are likely to deplete the ozone layer. Its production and use shall as a consequence be gradually phased out. It is therefore a main purpose of the present invention to identify, in view of their use as refrigerant media in refrigeration circuits and similar applications, azeotropic mixtures that do not contain any environmentally noxious fluids that are likely to be banned. According to a feature set forth in the hereto appended claim 1, the azeotropic mixtures that have been identified in this connection contain isobutane (also known as R600a in the trade) as a common component and a fluorinated hydrocarbon as an additional component, said components being invariably excluded from the list of substances that have to be banned according to the international regulations . The primary advantage offered by the azeotropic mixtures is commonly known to lie in the consistency of both pressure and temperature parameters during phase transition processes, ie. evaporation and condensation. Such a particular property eliminates the instability phenomena that take place inside heat exchangers and throttling elements, thereby making it much more easy to design the appliances. These and further advantages and features of the present invention will be more clearly understood from the following description which is given by way of non-limiting example with references to both the examples described in detail herein and the accompanying Tables 1 through to 6. As mentioned, the azeotropic mixtures to which the present invention refers are based on the use of isobutane (R600a) . These mixtures are pure azeotrope fluids, ie. fluids evaporating constantly at 20°C. Within the scope of the present invention fall of course all those mixtures which, while maintaining their components in each case unchanged, differ from each other for a different per-cent content of the same components in the mixture. These mixture behave like pure azeotrope fluids even under other temperature and pressure conditions differing fron the ones that are specifically indicated here; however, in refrigeration and also other applications they essentially behave as azeotrope fluids with respect to both their thermodynamic properties and the peculiarity of not segregating or fractionating during the boiling phase. First type of azeotropic mixture The basic composition of the mixture is the pure azeotrope which consists of 80-percent tetrafluoroethane [C 2 H 2 F 4 ] and 20-percent isobutane [ (CH 3 )2CHCH 3 ] at 20°C. This mixture has a boiling point of -33.35°C at a pressure of 0.1013 MPa. The composition range within which such a mixture does not deviate to any significant extent from a typical azeotropic behaviour may be defined by following percentages referred to the weight of the individual components: 50 to 95 weight- percent of tetrafluoroethane and 5 to 50 weight-percent of isobutane. In a preferred manner, the percent composition in weight of the mixture should be situated anywhere between 78 and 82 weight-percent of tetrafluoroethane and 18 and 22 weight-percent of isobutane. Such a mixture can be used in connection with refrigeration apparatuses operating on a compression and expansion cycle and, as compared with conventional refrigerant fluids, enables a smaller amount of fluid to be filled in the circuit and the energy usage of the equipment to be reduced. Furthermore, this mixture is effective in boosting the performance level of hermetic compressors with respect to the level achievable with the use of conventional refrigerant media. Finally, this mixture can be used in compressors in which mineral oil is filled as a lubricant. Experiments have been carried out, both in a compressor and a complete refrigeration apparatus, in view of testing the performance capabilities of this innovative mixture as compared with a conventional refrigerant. The most significant results of such experiments are summarized in the accompanying Tables 1 and 2. Specifically, Table 1 summarizes the results of a full set of calorimetric tests that have been carried out on a motor- driven compressor having a piston displacement volume of 5.7 c.c. From this Table it can be inferred that both the refrigerating capacity and the coefficient of performance are improved with respect to the corresponding values obtained by the same compressor when using tetrafluoroethane (R134a) as the refrigerant fluid, ie. the hitherto used substance that has been taken as the reference in this context. In particular, the increase in the coefficient of performance (COP) at the reference temperature of -23.3°C can be noticed to amount to approx. 10%. Table 2 summarizes the results of tests performed on a deep-freezer with a gross capacity of 222 litres. From the data appearing in said Table it can be noticed how the use of the mixture according to the present invention leads to a reduction in the charge of refrigerant filled in the refrigerating circuit, such a reduction amounting to approx. 30% with respect to the usual charge when employing tetrafluoroethane (R134a) and approx. 80% with respect to the usual charge when employing dichlorodifluoromethane (R12). Similarly, a reduction of approx. 4% with respect to tetrafluoroethane (Rl34a) and approx. 11% with respect to dichlorodifluoromethane (R12) has been obtained, while maintaining a practically constant average temperature in the storage compartment of the freezer. From the afore mentioned Tables it can further be noticed that the refrigerating capacity of the mixture according to the invention appears to be significantly greater than the one achievable with either R134a or R12. Further tests have been performed on a refrigeration machine provided with a hermetic compressor of the XKB-6 type manufactured in East-European countries, by using different percent compositions in weight of R134a and R600a, as compared to R134a alone, under following process conditions: boiling point 253°K (-20°C), condensation temperature 313°K (40°C), compressor suction temperature 305°K (32°C). Based on an analysis of the data appearing in the accompanying Table 3, it can be inferred that the refrigerant mixtures according to the invention show improved thermodynamic properties and, as a result, an improved thermodynamic efficiency. In particular, the refrigerating capacity appears to be improved by an extent ranging from 3 to 19% with respect to the reference refrigerant. Furthermore, the mixture according to the present invention is by no means harmful for the ozone layer in the stratosphere, since it basically uses R600a instead of R12. Second type of azeotropic mixture The basic composition of the mixture is the pure azeotrope which consists of 75-percent difluoroethane [C2H4F2] and 25- percent isobutane [ (CH 3 ) 2 CHCH 3 ] at 20°C. This mixture has a boiling point of -29.42°C at a pressure of 0.1013 MPa. The composition range within which such a mixture does not deviate to any significant extent from a typical azeotropic behaviour may be defined by following percentages referred to the weight of the individual components: 55 to 92 weight- percent of difluoroethane and 8 to 45 weight-percent of isobutane. In a preferred manner, the percent composition in weight of the mixture should be situated anywhere between 73 and 77 weight-percent of difluoroethane and 23 and 27 weight- percent of isobutane. Such a mixture can be used in connection with refrigeration apparatuses operating on a compression and expansion cycle and, as compared with conventional refrigerant fluids, enables a smaller amount of fluid to be filled in the circuit and the energy usage by the equipment to be reduced. Furthermore, this mixture is effective in boosting the performance level of hermetic compressors with respect to the level achievable with the use of conventional refrigerant media. Experiments have been carried out in view of testing the performance capabilities of this mixture on a motor-driven compressor for household refrigeration equipment. The most significant results of such experiments are summarized in the accompanying Table 4. Specifically, Table 4 summarizes the results of a full set of calorimetric tests that have been carried out on a motor- driven compressor having a piston displacement volume of 5.7 c.c. From this Table it can be inferred that both the refrigerating capacity and the coefficient of performance are improved with respect to the corresponding values obtained by the same compressor when using tetrafluoroethane (R134a) as the refrigerant fluid, ie. the hitherto used substance that has been taken as the reference in this context. In particular, the increase in the coefficient of performance (COP) at the reference temperature of -25% can be noticed to amount to approx. 8%. Even the refrigerating capacity is shown to be improved by as much as 13.6% over the one obtained when using R134a at the same evaporation temperature. Further tests have been performed on a refrigeration machine provided with a hermetic compressor of the XKB-6 type manufactured in East-European countries, by using different percent compositions in weight of R152a and R600a, as compared to a mixture of R152a and R12 (known also as R500 in the trade) in which the percentage in weight of R12 amounted to 74%, under following process conditions: boiling point 253°K (-20°C), condensation temperature 313°K (40°C), compressor suction temperature 305°K (32°C). Based on an analysis of the data appearing in the accompanying Table 5, it can be inferred that the refrigerant mixtures according to the invention show improved thermodynamic properties and, as a result, an improved thermodynamic efficiency. In particular, the refrigerating capacity appears to be improved by an extent ranging from 2 to 5% with respect to the reference refrigerant. Furthermore, the mixture according to the present invention is by no means harmful for the ozone layer in the stratosphere, since it basically uses RδOOa instead of R12. Third type of azeotropic mixture The composition of this mixture according to the invention is as follows: 95 to 98 weight-percent of an azeotropic mixture R507 and 2 to 5 weight-percent of isobutane (R600a) , wherein said azeotropic mixture R507 consists of 16.5 mole- percent of difluoroethane and 83.5 mole-percent of octafluoropropane (R218). Even this third type of mixture does not contain any fluid which might prove harmful for the ozone layer in the stratosphere and can be used in connection with refrigeration apparatuses operating on a compression and expansion cycle. Experiments have been performed on a refrigeration machine provided with a hermetic compressor of the XKB-6 type manufactured in East-European countries, by using different mole-percent compositions of the mixture, as compared to the R507 mixture alone, under following process conditions: boiling point 253°K (-20°C), condensation temperature 313°K (40°C), compressor suction temperature 305°K (32°C). Based on an analysis of the data appearing in the accompanying Table 6, it can be inferred that the refrigerant mixtures according to the invention show improved thermodynamic properties and, as a result, an improved thermodynamic efficiency. In particular, the refrigerating capacity appears to be improved by an extent ranging from 2 to 6% and the coefficient of performance by an extent ranging from 1 to 4% with respect to the reference refrigerant mixture. Conclusively, it will have been appreciated that the azeotropic mixtures to be used as refrigerant media according to the present invention are substances that do not prove harmful for the ozone layer and, at the same time, enable performance capabilities to be achieved which are clearly better than those obtainable by using conventional refrigerant fluids. It will further be appreciated that the afore illustrated mixtures may also be embodied with their components combined in any different composition as compared to the afore described ones, without departing from the scope of the present invention as defined in the appended claims.

Claims: CLAIMS 1. Refrigerant medium consisting of an azeotropic mixture, characterized in that it contains from 50 to 95 weight-percent of a fluorinated hydrocarbon and from 5 to 50 weight-percent of isobutane (CH 3 ) 2 CHCH 3 (R600a) . 2. Refrigerant medium according to claim 1, characterized in that said fluorinated hydrocarbon is tetrafluoroethane C 2 H 2 F 4* 3. Refrigerant medium according to claim 2, characterized in that it contains from 50 to 95 weight-percent of tetrafluoroethane and from 5 to 50 weight-percent of isobutane. 4. Refrigerant medium according to claim 3, characterized in that it contains from 78 to 82 weight-percent of tetrafluoroethane and from 18 to 22 weight-percent of isobutane. 5. Refrigerant medium according to claim 1, characterized in that said fluorinated hydrocarbon is difluoroethane C 2 H 4 F 2 . 6. Refrigerant medium according to claim 5, characterized in that it contains from 55 to 92 weight-percent of difluoroethane and from 8 to 45 weight-percent of isobutane. 7. Refrigerant medium according to claim 6, characterized in that it contains from 73 to 77 weight-percent of difluoroethane and from 23 to 27 weight-percent of isobutane. 8. Refrigerant medium according to claim 1, characterized in that said fluorinated hydrocarbon is an azeotropic mixture (R507) consisting of difluoroethane and octafluoropropane (R218) . 9. Refrigerant medium according to claim 8, characterized in that it contains from 95 to 98 weight-percent of R507 and from 2 to 5 weight-percent of isobutane.

Inventors: BELLOMO MATTEO, KHMELNJUCK MICHAEL G, LAVRENCHENKO GEORGI K, PLUGNIKOV OLEG, POL LANFRANCO, VOZNIJ VALERY, BELLOMO, MATTEO, KHMELNJUCK, MICHAEL G.;, LAVRENCHENKO, GEORGI K.;, PLUGNIKOV, OLEG;, POL, LANFRANCO, VOZNIJ, VALERY;
Applicants: BELLOMO MATTEO, KHMELNJUCK MICHAEL G, LAVRENCHENKO GEORGI K, PLUGNIKOV OLEG, POL LANFRANCO, VOZNIJ VALERY, ZANUSSI ELETTROMECC, BELLOMO, MATTEO, KHMELNJUCK, MICHAEL G.;, LAVRENCHENKO, GEORGI K.;, PLUGNIKOV, OLEG;, POL, LANFRANCO, VOZNIJ, VALERY;, ZANUSSI ELETTROMECCANICA S.P.A.
Application year: 1994
Main classification: C09K5
IPC codes: C09K5